CN105004712A - Method for constructing acetamiprid detection photoelectrochemical sensor and detecting method - Google Patents
Method for constructing acetamiprid detection photoelectrochemical sensor and detecting method Download PDFInfo
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- CN105004712A CN105004712A CN201510422603.5A CN201510422603A CN105004712A CN 105004712 A CN105004712 A CN 105004712A CN 201510422603 A CN201510422603 A CN 201510422603A CN 105004712 A CN105004712 A CN 105004712A
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Abstract
The invention discloses a method for constructing an acetamiprid detection photoelectrochemical sensor and a detection method, which comprises the steps of (1) regulating the molar ratio of Zn(Ac)22H2O to Co(Ac)24H2O in ethanol, and preparing Co-doped ZnO nanoparticles through the hydrothermal synthesis process; (2) cleaning and washing the ITO conductive glass, and airing the ITO conductive glass at the room temperature; (3) adding a Co-doped ZnO suspension liquid drop by drop onto the surface of an ITO electrode to prepare a Co-doped nano-ZnO film; (4) covering an acetamiprid aptamer onto the surface of the Co-doped nano-ZnO film to prepare an aptamer-based Co-doped ZnO photoelectrochemical sensor. According to the technical scheme of the invention, the acetamiprid and the aptamer are specifically bound together so as to cause the reduction of the photoelectric current. Based on the above principle, the quantitative detection is conducted. The invention has the advantages of simple equipment, simple and convenient method, good stability, high sensitivity and good selectivity.
Description
Technical field
The present invention relates to a kind of construction method and detection method of the Optical Electro-Chemistry sensor for Acetamiprid detection, belong to chemical analysis test field.
Background technology
Current Pesticide Residue causes the extensive concern of people, has jeopardized human health and cause environmental pollution because of it.Acetamiprid has become the substitute of organophosphorus pesticide or other common agricultural chemicals as a kind of anabasine insecticide, but it widely uses one of potential hazard material still becoming human health.The method of current detection Acetamiprid has: gas, liquid chromatography, colorimetric aptamer sensor, enzyme-linked immunosorbent assay and electrochemical process etc.But one or more following shortcomings all can be there are in often kind of method: apparatus expensive, method complexity, poor stability, consuming time, sensitivity is not high, selectivity is general.Therefore, seek conveniently, the Acetamiprid analytic approach of easy, quick, hypersensitive and high specific causes the interest of analytical work person.
Optical Electro-Chemistry detection is a kind of method of testing of novelty, the method is the separation causing electron-hole pair based on phot-luminescence telecommunications mark, under suitable inclined potential condition, realize electronics to transmit fast between thing, semiconductor and probe molecule in analysis, thus formation photocurrent, the existence analyzing thing can affect the change of photocurrent quantitatively, thus the Optical Electro-Chemistry realized analyzing thing detects.With regard to photoelectricity beacon, current design system mainly based on single semiconductor, such as: nano titanium oxide, cadmium sulfide, cadmium selenide, cadmium telluride, pyridine ruthenium, polythiofuran derivative etc.But single semiconductor due to light induced electron commute compound, thus suppresses the generation of photosignal and affects Optical Electro-Chemistry detection sensitivity further.Recently, can promote that the heterojunction semiconductor that charge carrier is effectively separated and local surface plasma technique are applied to Optical Electro-Chemistry sensing successively, but these methods have synthetic method complexity, the cycle is long, high in cost of production feature.Therefore, seek one-step synthesis doped semiconductor and newly mark as photoelectricity, and transition metal ion mix effective separation that can effectively promote charge carrier right, there is the features such as equipment is simple, easy to operate, cost is low.This technology is the striving direction building easy, quick, hypersensitive, high specific and environmental friendliness Optical Electro-Chemistry sensor.And the report of also unexposed Acetamiprid Optical Electro-Chemistry detection method in prior art, the Optical Electro-Chemistry detection method of Acetamiprid is still the blank on current technological layer.
Summary of the invention
Goal of the invention: the object of the invention is to for the deficiencies in the prior art, the construction method of the Optical Electro-Chemistry sensor providing a kind of Acetamiprid to detect.
The detection method that another object of the present invention is to provide a kind of Optical Electro-Chemistry sensor using above-mentioned Acetamiprid to detect to carry out Acetamiprid and quantitatively detect.
Technical scheme: the construction method of a kind of Optical Electro-Chemistry sensor for Acetamiprid detection of the present invention, comprises the steps:
(1) Zn (Ac) is regulated in ethanol
22H
2o and Co (Ac)
24H
2the mol ratio of O, makes Co
2+with Zn
2+mol ratio be 0.5 ~ 4.0%, (the Co hereinafter related to
2+mol ratio all refers to Co
2+with Zn
2+molar ratio), adopt hydrothermal synthesis method prepare Co-doped ZnO nano particle;
(2) ITO electro-conductive glass is cleaned, flushing operation at room temperature drying;
(3) be prepared into suspending liquid by Co-doped ZnO nanoparticle dispersion to water, drop to ITO electrode surface, make cobalt doped Nano zinc oxide film;
(4) be 1 ~ 3nmolL by concentration
-1acetamiprid aptamer covers the surface of cobalt doped Nano zinc oxide film, prepares aptamer base Co-doped ZnO Optical Electro-Chemistry sensor.
Preferably, the preparation method of described Co-doped ZnO nano particle is specially: first by 50ml 1molL
-1naOH solution dropwise add 100ml Co
2+with Zn
2+mol ratio be 0.5 ~ 4.0% Zn (Ac)
22H
2o and Co (Ac)
24H
2in O solution, at room temperature magnetic agitation reaction 30 ~ 60 minutes; Then mixed liquor is transferred in autoclave and continues to heat 2 hours under 110 ~ 130 DEG C of conditions, be cooled to room temperature; Last centrifugal collecting precipitate, with absolute ethyl alcohol and pure water cross washing sediment 3 ~ 5 times, the sediment after washing is dry under 110 ~ 130 DEG C of conditions.
Preferably, Co described in step (1)
2+mol ratio is 1%, and the photocurrent produced under this ratio is maximum.
Preferably, carry out cleaning the mixed solvent that the clean-out system used is ammoniacal liquor, hydrogen peroxide and water volume ratio are 1 ~ 3:1 ~ 3:50 to ITO electro-conductive glass in step (2).
Preferably, described in step (3), the concentration of Co-doped ZnO nanoparticle suspension is 0.8 ~ 1.2mgml
-1.
Preferably, described in step (3), the preparation method of cobalt doped Nano zinc oxide film is: by the Co-doped ZnO hanging drop of 20 μ L to ITO electrode surface, form the round spot that diameter is 5mm, uniform film is obtained after drying in saturated atmosphere, by film thermal treatment 1 hour under 250 ~ 350 DEG C of conditions, be cooled to room temperature, obtain cobalt doped Nano zinc oxide film.
Preferably, the preparation method of the Optical Electro-Chemistry of aptamer base Co-doped ZnO described in step (4) sensor is: be 1 ~ 3nmolL by 10 μ L concentration
-1acetamiprid aptamer cover the surface of cobalt doped Nano zinc oxide film, incubation 30 minutes under 35 ~ 40 DEG C of conditions, then wash away combination Acetamiprid aptamer loosely with phosphate buffer, obtain aptamer base Co-doped ZnO Optical Electro-Chemistry sensor.
Described in step (4), the base sequence of aptamer is:
5'-TGTAATTTGTCTGCAGCGGTTCTTGATCGCTGACACCAT ATTATGAAGA-3'。
The detection method of the Optical Electro-Chemistry sensor for Acetamiprid detection described in the present invention comprises the steps:
(1) with the aptamer modified Co-doped ZnO electrode of Acetamiprid for light anode, set up aptamer based photoelectrochemicalcell standard measure and detect Acetamiprid;
(2) above-mentioned smooth anode is placed in the phosphate buffer that pH is 7, in damping fluid, adds 0.1molL
-1quercetin and Acetamiprid are tested, and record adds the curent change of Co-doped ZnO base light anode before and after Acetamiprid;
(3) according to the Acetamiprid concentration-photocurrent quantitative relationship equation drafted, the concentration of Acetamiprid in medicine to be measured is calculated.
Preferably, the volume range of the Quercetin added in step (3) is 30 μ L ~ 150 μ L.
Testing result show, along with the increase of measured object Acetamiprid concentration, photocurrent is reduction trend, and within the scope of finite concentration linear relation.Under Acetamiprid existence condition, aptamer, specifically in conjunction with Acetamiprid, makes electrode surface resistance increase, and causes Quercetin to be difficult to arrive electrode surface, so its photocurrent declines, can extrapolate the concentration of Acetamiprid according to the degree of photocurrent decline.
Beneficial effect: (1) the present invention adopts the Co of one-step synthesis method ultra-fine grain diameter
2+nanometer doped zinc oxide as photoelectricity beacon, and passes through regulation and control adulterant Co
2+ratio, make Co
2+mol ratio is 0.5 ~ 4.0%, prepares the photoelectricity beacon of excellent performance, improves Optical Electro-Chemistry detection sensitivity, especially works as Co
2+mol ratio when being 1%, photocurrent is maximum, effectively can be detected by the change of photocurrent to Acetamiprid concentration; (2) prepare Acetamiprid aptamer base Co-doped ZnO Optical Electro-Chemistry sensor equipment used in the present invention simple, also there is no complicated sample handling processes, there is cost low, easily make, the advantage that efficiency is high.(3) detection mechanism of the present invention is the specific effect based on Acetamiprid aptamer corresponding to it, and through experimental identification, eliminates the interference of other Common drugs, improves the selectivity that its photoelectrochemical method detects.
Accompanying drawing explanation
Fig. 1 is the structure schematic diagram of Acetamiprid aptamer based photoelectrochemicalcell sensor;
Fig. 2 is the transmission electron microscope photo of zinc oxide nano-particle (A) and 1% mol ratio Co-doped ZnO nano particle (B);
Fig. 3 is x-ray diffraction pattern (A) and the UV-Vis diffuse reflection spectroscopy figure (B) of zinc oxide nano-particle (a) and 1% mol ratio Co-doped ZnO nano particle (b); Be zinc oxide nano-particle on the left of illustration in figure (B), right side is 1% mol ratio Co-doped ZnO nanoparticle suspension;
Fig. 4 is that the x-ray photoelectron spectroscopy of 1% mol ratio Co-doped ZnO nano particle (A) is always schemed, and (B, C, D, E) is respectively the x-ray photoelectron spectroscopy figure of zinc, cobalt, charcoal, oxygen chemical state separately;
Fig. 5 is different Co
2+mol ratio (the photocurrent curve (A) of a, b, c, d, e, f, g represent respectively (0%, 0.5%, 1.0%, 1.5%, 2.0%, 3.0%, 4.0%) nanometer doped zinc oxide; Different volumes (a, b, c, d, e represent 30 μ L respectively, 50 μ L, 70 μ L, 100 μ L, 150 μ L) 0.1mol L
-1quercetin sensitization 1% mol ratio cobalt is mixed zinc paste photocurrent curve;
Fig. 6 is that (a, b are zinc paste optoelectronic pole to different optoelectronic pole; C, d are that cobalt is mixed zinc oxide electrode; E, f are that aptamer modified 1.0% cobalt of Acetamiprid is mixed zinc oxide electrode; Wherein a, c electrode detects in pH 7 phosphate buffer; B, d, e electrode contains 50 μ L 0.1molL at pH 7 phosphate buffer
-1detect in Quercetin; F electrode contains 50 μ L 0.1molL at pH 7 phosphate buffer
-1quercetin and 40nmolL
-1detect in Acetamiprid) photocurrent curve (A); Common agricultural chemicals detects the interference (B) of Acetamiprid to this method;
Fig. 7 is the quantitative relationship that aptamer based photoelectrochemicalcell method detects Acetamiprid: figure A is the increase along with measured object Acetamiprid concentration, and photocurrent is reduction trend; Figure B is its quantitative relationship fit equation figure.
Embodiment
Below by accompanying drawing, technical solution of the present invention is described in detail, but protection scope of the present invention is not limited to described embodiment.
Embodiment 1: a kind of construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection, comprises the steps:
(1) first by 50ml 1molL
-1naOH solution dropwise add the Co of 100ml
2+mol ratio is the Zn (Ac) of 1%
22H
2o and Co (Ac)
24H
2in O solution, at room temperature magnetic agitation reacts 30 minutes; Then mixed liquor is transferred in autoclave and continues to heat 2 hours under 120 DEG C of conditions, be cooled to room temperature; Last centrifugal collecting precipitate, with absolute ethyl alcohol and pure water cross washing sediment 4 times, the sediment after washing is dry under 120 DEG C of conditions, obtained Co-doped ZnO nano particle;
(2) ITO electro-conductive glass is cut into the size of 1cm × 4cm, and uses the mixed solution that ammoniacal liquor, hydrogen peroxide and water volume ratio are 1:1:50 to clean, then rinse well to be placed in air with water and dry use to be prepared.
(3) by 20 μ L 1mgml
-1co-doped ZnO hanging drop to ITO electrode surface, forming diameter is the round spot of 5mm, obtains uniform film after drying in saturated atmosphere, by film thermal treatment 1 hour under 300 DEG C of conditions, is cooled to room temperature, obtains cobalt doped Nano zinc oxide film.
(4) be 1nmolL by 10 μ L concentration
-1acetamiprid aptamer cover the surface of cobalt doped Nano zinc oxide film, the base sequence of described aptamer is
5'-TGTAATTTGTCTGCAGCGGTTCTTGATCGCTG ACACCATATTATGAAGA-3', incubation 30 minutes under 37 DEG C of conditions, then wash away combination Acetamiprid aptamer loosely with phosphate buffer, obtain aptamer base Co-doped ZnO Optical Electro-Chemistry sensor.
Fig. 2 is the transmission electron microscope photo of zinc oxide nano-particle (A) and 1% mol ratio Co-doped ZnO nano particle (B) in the implementation case, can find out that from (A) figure the size of nano zinc oxide particles is at 15 ran, and the size of 1% mol ratio Co-doped ZnO nano particle is at 8 ran in right figure, this mixes due to cobalt the formation hindering zinc oxide nano-particle.
Fig. 3 is x-ray diffraction pattern (A) and the UV-Vis diffuse reflection spectroscopy figure (B) of zinc oxide nano-particle (a) and 1% mol ratio Co-doped ZnO nano particle (b) in the present embodiment; Be zinc oxide nano-particle on the left of illustration in figure (B), right side is 1% mol ratio Co-doped ZnO nanoparticle suspension.Upper as can be seen from the diffractogram (A) of zinc oxide nano-particle, the position of its diffraction peak is consistent with its standard card numerical value, and there is no other impurity peaks, illustrate and successfully synthesized nano zine oxide, the cobalt doped of 1% mol ratio does not change the crystal formation of nano zine oxide, so the position of its diffraction peak and intensity there are not change substantially; But can find out that the cobalt doped of 1% mol ratio causes its absorption edge red shift from both UV-Vis diffuse reflection spectroscopy figure (B), and within the scope of 200-800, have stronger absorption, illustrate that cobalt successfully instead of the position of zinc, result in its band gap and narrow.
In Fig. 4, A is that the x-ray photoelectron spectroscopy of zinc oxide nano-particle in the present embodiment is always schemed, and wherein schemes the x-ray photoelectron spectroscopy figure that B, C, D, E are respectively zinc, cobalt, charcoal, oxygen chemical state separately.As can be seen from figure A, all peaks are attributed to zinc, cobalt, oxygen, charcoal, do not find other impurity peaks; As can be seen from figure B, C, D, E, the combination of each element can correspond to respective chemical state, and the swarming standard drawing of each element is consistent, and again proves to synthesize Co-doped ZnO to merit, and wherein carbon comes from the carbon dioxide in air.
The detection method of a kind of Optical Electro-Chemistry sensor for Acetamiprid detection described in the present invention, comprises the steps:
(1) with the aptamer modified Co-doped ZnO electrode of Acetamiprid for light anode, set up aptamer based photoelectrochemicalcell standard measure and detect Acetamiprid;
(2) above-mentioned smooth anode is placed in the phosphate buffer that pH is 7, in damping fluid, adds the 0.1molL that volume is 50 μ L
-1quercetin and Acetamiprid are tested, and record adds the curent change of Co-doped ZnO base light anode before and after Acetamiprid;
(3) according to the Acetamiprid concentration-photocurrent quantitative relationship equation drafted, the concentration of Acetamiprid in testing sample is extrapolated.
Testing result show, along with the increase of measured object Acetamiprid concentration, photocurrent is reduction trend, and within the scope of finite concentration linear relation.
In order to verify whether other common pesticides exist interference to the detection method of the Acetamiprid in the present invention, in test fluid, add isoconcentration Prochloraz, dichlofenthion, tribenuron-methyl, Flusilazole and Imidacloprid respectively, control test is carried out according to above-mentioned steps.
Fig. 6 is that (a, b are zinc paste optoelectronic pole to different optoelectronic pole; C, d are that cobalt is mixed zinc oxide electrode; E, f are that the aptamer modified 1.0mol% cobalt of Acetamiprid is mixed zinc oxide electrode; Wherein a, c electrode detects in pH 7 phosphate buffer; B, d, e electrode contains 50 μ L 0.1molL at pH 7 phosphate buffer
-1detect in Quercetin; F electrode contains 50 μ L 0.1molL at pH 7 phosphate buffer
-1quercetin and 40nmolL
-1detect in Acetamiprid) photocurrent curve (A); Common agricultural chemicals detects the interference (B) of Acetamiprid to this method, A (a, b from the graph; C, d) curve can find out, 50 μ L 0.1molL
-1quercetin can promote to shift electronically as electron donor effectively, and photo-signal is amplified; The introducing of Acetamiprid aptamer causes electron transfer efficiency to decline, and causes photocurrent slightly to decline; Under Acetamiprid existence condition, photocurrent continuation decline is attributable to aptamer and in conjunction with Acetamiprid, electrode surface resistance is increased specifically, causes Quercetin to be difficult to arrive electrode surface, so its photocurrent declines.Based on this principle, this sensor can be used for Acetamiprid ground and quantitatively detects.B can find out from the graph, and the common agricultural chemicals of equimultiple affects the quantitative detection of Acetamiprid hardly, and the method has fabulous selectivity.
Fig. 7 is that aptamer based photoelectrochemicalcell standard measure detects Acetamiprid: figure A is the increase along with measured object Acetamiprid concentration, and photocurrent is reduction trend; Figure B is its quantitative relationship fit equation figure.
Embodiment 2: a kind of construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection, comprises the steps:
(1) first by 50ml 1molL
-1naOH solution dropwise add the Co of 100ml
2+mol ratio is the Zn (Ac) of 0.5%
22H
2o and Co (Ac)
24H
2in O solution, at room temperature magnetic agitation reacts 40 minutes; Then mixed liquor is transferred in autoclave and continues to heat 2 hours under 110 DEG C of conditions, be cooled to room temperature; Last centrifugal collecting precipitate, with absolute ethyl alcohol and pure water cross washing sediment 3 times, the sediment after washing under 110 DEG C of conditions, obtained Co-doped ZnO nano particle;
(2) ITO electro-conductive glass is cut into the size of 1cm × 4cm, and uses the mixed solution that ammoniacal liquor, hydrogen peroxide and water volume ratio are 2:2:50 to clean, then rinse well to be placed in air with water and dry use to be prepared.
(3) by 20 μ L 1mgml
-1co-doped ZnO hanging drop to ITO electrode surface, forming diameter is the round spot of 5mm, obtains uniform film after drying in saturated atmosphere, by film thermal treatment 1 hour under 250 DEG C of conditions, is cooled to room temperature, obtains cobalt doped Nano zinc oxide film.
(4) be 2nmolL by 10 μ L concentration
-1acetamiprid aptamer cover the surface of cobalt doped Nano zinc oxide film, the base sequence of described aptamer is
5'-TGTAATTTGTCTGCAGCGGTTCTTGATCGCTGACACCATATTATGAAGA-3', incubation 30 minutes under 35 DEG C of conditions, then wash away combination Acetamiprid aptamer loosely with phosphate buffer, obtain aptamer base Co-doped ZnO Optical Electro-Chemistry sensor.
The detection method of a kind of Optical Electro-Chemistry sensor for Acetamiprid detection described in the present invention, comprises the steps:
(1) with the aptamer modified Co-doped ZnO electrode of Acetamiprid for light anode, set up aptamer based photoelectrochemicalcell standard measure and detect Acetamiprid;
(2) above-mentioned smooth anode is placed in the phosphate buffer that pH is 7, in damping fluid, adds the 0.1molL that volume is 30 μ L
-1quercetin and Acetamiprid are tested, and record adds the photocurrent variations of Co-doped ZnO base light anode before and after Acetamiprid;
(3) according to the Acetamiprid concentration-photocurrent quantitative relationship equation drafted, the concentration of Acetamiprid in testing sample is extrapolated.
Testing result show, along with the increase of measured object Acetamiprid concentration, photocurrent is reduction trend, and within the scope of finite concentration linear relation.In order to verify whether other common pesticides exist interference to the detection method of the Acetamiprid in the present invention, in test fluid, add isoconcentration Prochloraz, dichlofenthion, tribenuron-methyl, Flusilazole and Imidacloprid respectively, control test is carried out according to above-mentioned steps.
Embodiment 3: a kind of construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection, comprises the steps:
(1) first by 50ml 1molL
-1naOH solution dropwise add the Co of 100ml
2+the Zn (Ac) of mol ratio 4%
22H
2o and Co (Ac)
24H
2in O solution, at room temperature magnetic agitation reacts 60 minutes; Then mixed liquor is shifted in autoclave and continue to heat 2 hours under 130 DEG C of conditions, be cooled to room temperature; Last centrifugal collecting precipitate, with absolute ethyl alcohol and pure water cross washing sediment 5 times, the sediment after washing is dry under 130 DEG C of conditions, obtained Co-doped ZnO nano particle;
(2) ITO electro-conductive glass is cut into the size of 1cm × 4cm, and uses the mixed solution that ammoniacal liquor, hydrogen peroxide and water volume ratio are 3:3:50 to clean, then rinse well to be placed in air with water and dry use to be prepared.
(3) by 20 μ L 1mgml
-1co-doped ZnO hanging drop to ITO electrode surface, forming diameter is the round spot of 5mm, obtains uniform film after drying in saturated atmosphere, by film thermal treatment 1 hour under 350 DEG C of conditions, is cooled to room temperature, obtains cobalt doped Nano zinc oxide film.
(4) be 3nmolL by 10 μ L concentration
-1acetamiprid aptamer cover the surface of cobalt doped Nano zinc oxide film, the base sequence of described aptamer is
5'-TGTAATTTGTCTGCAGCGGTTCTTGATCGCTGACACCATATTATGAAGA-3', incubation 30 minutes under 40 DEG C of conditions, then wash away combination Acetamiprid aptamer loosely with phosphate buffer, obtain aptamer base Co-doped ZnO Optical Electro-Chemistry sensor.
The detection method of a kind of Optical Electro-Chemistry sensor for Acetamiprid detection described in the present invention, comprises the steps:
(1) with the aptamer modified Co-doped ZnO electrode of Acetamiprid for light positive electrode, set up aptamer based photoelectrochemicalcell standard measure and detect Acetamiprid;
(2) above-mentioned smooth anode is placed in the phosphate buffer that pH is 7, in damping fluid, adds the 0.1molL that volume is 150 μ L
-1quercetin and Acetamiprid are tested, and record adds the photocurrent variations of Co-doped ZnO base light anode before and after Acetamiprid;
(3) according to the Acetamiprid concentration-photocurrent quantitative relationship equation drafted, the concentration of Acetamiprid in testing sample is extrapolated.
Testing result show, along with the increase of measured object Acetamiprid concentration, photocurrent is reduction trend, and within the scope of finite concentration linear relation.In order to verify whether other common pesticides exist interference to the detection method of the Acetamiprid in the present invention, in test fluid, add isoconcentration Prochloraz, dichlofenthion, tribenuron-methyl, Flusilazole and Imidacloprid respectively, control test is carried out according to above-mentioned steps.
As mentioned above, although represented with reference to specific preferred embodiment and described the present invention, it shall not be construed as the restriction to the present invention self.Under the spirit and scope of the present invention prerequisite not departing from claims definition, various change can be made in the form and details to it.
Claims (10)
1., for a construction method for the Optical Electro-Chemistry sensor of Acetamiprid detection, it is characterized in that comprising the steps:
(1) Zn (Ac) is regulated in ethanol
22H
2o and Co (Ac)
24H
2the mol ratio of O, makes Co
2+with Zn
2+mol ratio be 0.5 ~ 4.0%, adopt hydrothermal synthesis method prepare Co-doped ZnO nano particle;
(2) ITO electro-conductive glass is cleaned, flushing operation at room temperature drying;
(3) be prepared into suspending liquid by Co-doped ZnO nanoparticle dispersion to water, drop to ITO electrode surface, make cobalt doped Nano zinc oxide film;
(4) be 1 ~ 3nmolL by concentration
-1acetamiprid aptamer covers the surface of described cobalt doped Nano zinc oxide film, prepares aptamer base Co-doped ZnO Optical Electro-Chemistry sensor.
2. the construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 1, it is characterized in that, described in step (1), the preparation method of Co-doped ZnO nano particle is: first by 50ml 1molL
-1naOH solution dropwise add 100ml Co
2+with Zn
2+mol ratio be 0.5 ~ 4.0% Zn (Ac)
22H
2o and Co (Ac)
24H
2in O solution, at room temperature magnetic agitation reaction 30 ~ 60 minutes; Then mixed liquor is transferred in autoclave and continues to heat 2 hours under 110 ~ 130 DEG C of conditions, be cooled to room temperature; Last centrifugal collecting precipitate, with absolute ethyl alcohol and pure water cross washing sediment 3 ~ 5 times, the drying under 110 ~ 130 DEG C of conditions of the sediment after washing obtains.
3. the construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 1 and 2, is characterized in that: described Co
2+with Zn
2+mol ratio be 1%.
4. the construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 1, it is characterized in that, carry out cleaning the mixed solvent that the clean-out system used is ammoniacal liquor, hydrogen peroxide and water volume ratio are 1 ~ 3:1 ~ 3:50 to ITO electro-conductive glass in step (2).
5. the construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 1, it is characterized in that, described in step (3), the concentration of Co-doped ZnO nanoparticle suspension is 0.8 ~ 1.2mgml
-1.
6. the construction method of a kind of Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 1, it is characterized in that, described in step (3), the preparation method of cobalt doped Nano zinc oxide film is: by 20 μ L Co-doped ZnO hanging drops to ITO electrode surface, form the round spot that diameter is 5mm, uniform film is obtained after drying in saturated atmosphere, by film thermal treatment 1 hour under 250 ~ 350 DEG C of conditions, be cooled to room temperature, obtain cobalt doped Nano zinc oxide film.
7. the construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 1, it is characterized in that, the preparation method of the Optical Electro-Chemistry of aptamer base Co-doped ZnO described in step (4) sensor is: the surface Acetamiprid aptamer of 10 μ L being covered cobalt doped Nano zinc oxide film, incubation 30 minutes under 35 ~ 40 DEG C of conditions, then wash away combination Acetamiprid aptamer loosely with phosphate buffer, obtain aptamer base Co-doped ZnO Optical Electro-Chemistry sensor.
8. the construction method of the Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 1, described in step (4), the base sequence of aptamer is
5'-TGTAATTTGTCTGCAGCGGTTCTTGATCGCTGACACCATATTATGAAGA-3'。
9. the detection method of the Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 1, is characterized in that comprising the steps:
(1) with the aptamer modified Co-doped ZnO electrode of Acetamiprid for light positive electrode, set up aptamer based photoelectrochemicalcell standard measure and detect Acetamiprid;
(2) above-mentioned smooth anode is placed in the phosphate buffer that pH is 7, in damping fluid, adds 0.1molL
-1quercetin and Acetamiprid are tested, and record adds the photocurrent variations of Co-doped ZnO base light anode after Acetamiprid;
(3) according to the Acetamiprid concentration-photocurrent quantitative relationship equation drafted, the concentration of Acetamiprid in medicine to be measured is calculated.
10. the detection method of the Optical Electro-Chemistry sensor for Acetamiprid detection according to claim 9, is characterized in that the volume of the Quercetin added in step (2) is 30 μ L ~ 150 μ L.
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| CN107655958A (en) * | 2017-09-22 | 2018-02-02 | 山西大学 | Acetamiprid detection method based on ferronickel cyanide complex nano particle for instruction probe |
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| CN112098485B (en) * | 2020-09-16 | 2022-11-01 | 山东科技大学 | Photoelectrochemical aptamer sensor based on sensing separation strategy and preparation method and application thereof |
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